Magenta phenazonium dyestuff images from 8-hydroxyquinoline couplers



Patented Oct. 3., 1950 MAGENTA PI-IENAZONIUM DYESTUFF IM- AGES FROM S-HYDROXYQUINOLINE COUPLERS Robert F. Coles, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware N Drawing. Application December 23, 1947,

Serial No. 793,536 6 6 Claims.

T The present invention relates to color formers of the 8-hydroxyquinoline class, which are particularly suitable for the production of magenta phenazonium dyestuff images by color development of an exposed silver halide emulsion with an orthophenylene diamine type color developer.

In the copending application Serial No. 640,382, filed On January 10, 1946, of Willy A. Schmidt and Vsevolod Tulagin, now Patent No. 2,486,440, there is described the production of phenazonium 'dyestuff images by color developing an exposed silver halide emulsion with a color developer comprising an ortho-phenylene diamine in the presence of a color former which may be inter alia 8-hydroxyquinoline.

It has now been discovered that the method of said application can be practiced to yield phenazonium dyestuff images having a markedly improved magenta transmission spectra by utilizing as the color formers S-hydroxyquinolines (including 8-hydroxy cinchoninic acids) containing in the 2 position of the nucleusthereof an electronegative substituent such as a halogen or a mononuclear carbocyclic aromatic radical. It has been further found that such compounds readily lend themselves to the introduction of long alkyl chains to thereby render the color formers non-migratory in photographic emulsions, thus facilitating the employment of'the picted by the following structural formula:

wherein R is an electronegative group such as a halogen, i. e., chlorine or bromine, or a mononuclear carbocyclic aromatic radical such as phenyl, nitro-phenyl, amino-phenyl, alkyl-sulfonamido-phenyl, alkyl-carboxamido-phenyl, in

which if desired the alkyl radical may contain 10 or more carbon atoms, and the like, and R represents hydrogen, carboxy, or a carboxamido group containing an alkyl chain of at least 10,

carbon atoms, such as tetradecanoylamino, decanoylamino, dodecanoylamino, stearoylamino, and the like, or acylaminoaryl-carbamyl, such as stearoylamino benzene carbamyl, stearoyl- 5 methyl-sulfobenzene-carbamyl, and the like.

Examples of compounds embraced by the above formula are the following:

2-chloro-8-hydroxyquino1ine 2. OOOH OH 2-phenyl-8-hydroxy-cinchoninic acid 3. o 0 OH i I? NS mHzi N 7 1 O V H 2- (3-decylsulfonamidophenyl)-8-hydroxy cinchoninic acid 4. O O OH t I? N-fi-O12H25 2-(3-dodecylsulfonamidophenyl)-8-hydroxy cinchoninic acid Br N 60 v 2-bromo-8-hydroxy-quinoline H e 2 (3 -nitrophenyl) -8-hy droxy-quin oline 2 (3-aminophenyl) -8-hydroxy-quinoline 2-(3-myristoylaminophenyl)-8-hydroxy cinchoninic acid 9. C O OH Br N 611 2-bromo-8-hydroxy cinchoninic acid CzH4SO3H C1s a1 (Shydroxy-Z-phenylcinchoninoyl) -octadecy1tau rine I S OaH 7 -stearoylamino-3- (8-hydroxy-2-phenylcinchoninoyl) amino-4-toluenesulfonic acid persed in the photographic emulsions in order.

to be operable to produce the desired images on color forming development.

The color developers, which are utilized are as stated of the ortho-phenylenediamine class, a large number of examples of which are referred to in the aforesaid Schmidt and Tulagin application. Suitable color developers are, for example: 4,6-dianilino metanilic acid, 4,6-bis-(omethoxy-phenylamino) metanilic acid, 4-(ncarboxy-phenylamino)- fi-(p-methoxy-phenylamino) phenylamino)-metanilic acid, and the like.

It is to be understood that the crux of the present invention is the color formers, and that any ortho-phenylene diamine tylpe developer may be used "with the color formers in producing the desired magenta phenazonium dye images.

The majority of the color formers previously referred to are known compounds. Those which are not described in the literature, such as that of Exam les 3, 4, 8 and 11, can be prepared by the usual amidation reaction. For instance, the compound No. 3 may be obtained by reacting 2- metanilic acid, 4,6-bis-(p-methoxy- (3-aminophenyl) -8-hydroxy cinchoninic acid with decyl sulfonyl chloride in the presence of an acid-binding agent such as pyridine. A similar procedure is employed in producing the compound No. 4, the only difference being that lauryl sulfonyl chloride is used in forming the sulfonamide.

Compound No. 8 may be prepared by reacting 2-(3-amino-phenyl)S-hydroxy cinchoninic acid with myristoyl chloride in the presence of an acid-binding agent such as pyridine.

Compound No. 10 may be formed by treating equimolecular proportions of 2-phenyl-8-hydroxy cinchoninic acid and octadecyl-taurine in pyridine solution with an excess of phosphorus trichloride dissolved in pyridine.

Compound No. 11 is formed by treating equimolecular proportions of 2-phenyl-8-hydroxy cinchoninic acid and 3-amino-6-stearoylamino- 4-toluenesulfonic acid in pyridine with an excessof phosphorus trichloride dissolved in pyridine.

The invention is illustrated by the following examples, but it is to be understood that these examples are illustrative and not limitative of the invention.

Ewample 1 A photographic silver bromide emulsion is exposed and then color developed for five to ten minutes in a solutionv of the following color developer:

Sodium carbonate monohydrate grams 60 Potassium bromide do 2.5 Sodium sulfite do 40 Pyridine cc. 12 4,6-dianilino metanilic acid grams 4 2-chloro-8-hydroxyquinoline do 2 Water cc. 1000 The developed silver image is bleached with potassium ferricyanide and fixed in an acid hardening hypo solution. There is thus obtained a phenazonium dyestufi image which has a hig magenta transmission spectrum.

Example 2 .5 gram of 2-(3-decylsulfonamidophenyl) -8- hydroxy cinchoninic acid is dissolved in 10 ml. of water by the addition of 1 Nsodium hydroxide solution. The solution of the color former is then added to 50 grams of a silver bromide emulsion and the emulsion coated on a iilm base.

The film after drying is exposed and developed with the developer of Example 1, excepting that the. 2-ch1oro-8-hydroxyquinoline is omitted from the developing solution.

After working up the film as in. Example 1, there is obtained a brilliant magenta dyestuff image having a high spectral transmission.

Example 3 emulsion with a 2,4-diamino aniline developer in the presence of a color former having the following formula:

in which R is an electronegative radical selected from the class consisting of halogen and a mononuclear carbocyclic aromatic radical, and R is a member of the class consisting of hydrogen, carboxy and carbonamido groups containing an alkyl chain of at least carbon atoms.

2. A photographic developer for the production of magenta phenazonium dyestuff images com prising an alkaline solution containing as its essential components a 2,4-diamino aniline developer and as the color former a compound of the following formula: I

in which R is an electronegative radical selected from the class consisting of halogen and a mononuclear carbocyclic aromatic radical, and R is a member of the class consisting of hydrogen, carboxy and carbonamido groups containing an alkyl chain of at least 10 carbon atoms.

3. A photographic silver halide emulsion con- 7 taining as a color former capable of yielding magenta phenazonium dyestufi images a compound of the following formula:

in which R is an electronegative radical selected from the class consisting of halogen and a mononuclear carbocyclic aromatic radical, and R is a member of the class consisting of hydrogen, carboxy and carbonamido groups containing an alkyl chain of at least 10 carbon atoms, at least one of the radicals R and R containing an alkyl chain of at least 10 carbon atoms.

4. The process as defined in claim 1 wherein the color former is 2-chloro-8-hydroxyquinoline.

5. The photographic developer defined in claim 2 wherein the color former is 2-chloro-8-hydroxyquinoline.

6. A'photographic silver halide emulsion containing as a color former 5-stearoylamino-3-(8- hydroxy 2 phenylcinchoninoyl) -amino-4-to1- uenesulfonic acid.

ROBERT F. COLES.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date 

1. THE PROCESS OF PRODUCING MAGENTA PHENAZONIUM DYESTUFF IMAGES IN AN EXPOSED SILVER HALIDE EMULSION WHICH COMPRISES DEVELOPING SAID EMULSION WITH A 2,4-DIAMINO ANILINE DEVELOPER IN THE PRESENCCE OF A COLOR FORMER HAVING THE FOLLOWING FORMULA: 